EP3149110B1 - Liquid crystal medium - Google Patents

Description

enthält,
und
zusätzlich eine oder mehrere Verbindungen ausgewählt aus der Gruppe der Verbindungen der Formeln IIA, IIB und IIC,

worin

R^2A, R^2B und R^2C

jeweils unabhängig voneinander H, einen unsubstituierten, einen einfach durch CN oder CF₃ oder mindestens einfach durch Halogen substituierten Alkyl- oder Alkenylrest mit bis zu 15 C-Atomen, wobei in diesen Resten auch eine oder mehrere CH₂-Gruppen durch -O-, -S-,

-C≡C-, -CF₂O-, -OCF₂-, -OC-O- oder -O-CO- so ersetzt sein können, dass O-Atome nicht direkt miteinander verknüpft sind,

L^1-4

jeweils unabhängig voneinander F, Cl, CF₃ oder CHF₂,

Z² und Z^2'

jeweils unabhängig voneinander Einfachbindung, -C≡C-, -CH₂CH₂-, -CH=CH-, -CF₂O-, -OCF₂-, -CH₂O-, -OCH₂-, -COO-, -OCO-, -C₂F₄-, -CF=CF-, -CH=CHCH₂O-,

p

0, 1 oder 2,

q

0 oder 1, und

v

1 bis 6

bedeuten,
enthält.The invention relates to a liquid-crystalline medium according to claim 1, which is the compound of formula I-1 and / or the compound of formula I-2

contains
and
additionally one or more compounds selected from the group of the compounds of the formulas IIA, IIB and IIC,

wherein

R ^2A , R ^2B and R ^2C

in each case independently of one another H, an unsubstituted alkyl or alkenyl radical having up to 15 carbon atoms which is monosubstituted by CN or CF ₃ or at least monosubstituted by halogen, where one or more CH ₂ groups in these radicals are also represented by -O-, -S-,

-C≡C, -CF ₂ O-, -OCF ₂ -, -OC-O- or -O-CO- may be replaced so that O atoms are not directly linked to one another,

L ^1-4

each independently of one another F, Cl, CF ₃ or CHF ₂ ,

Z ² and Z ^{2 '}

each independently of one another single bond, -C≡C-, -CH ₂ CH ₂ -, -CH = CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF = CF-, -CH = CHCH ₂ O-,

p

0, 1 or 2,

q

0 or 1, and

v

1 to 6

mean,
contains.

Such media are to be used in particular for electro-optical displays with an active-matrix addressing based on the ECB effect as well as for in-plane switching or Fringe Field Switching (FFS) displays.

The principle of electrically controlled birefringence, the ECB effect (electrically controlled birefringence) or the DAP effect (deformation of upright phases) was first described in 1971 ( MF Schieckel and K. Fahrenschon, "Deformation of nematic liquid crystals with vertical orientation in electrical fields", Appl. Phys. Lett. 19 (1971), 3912 ). It followed Works by JF Kahn (Appl Phys Physic Lett 20 (1972), 1193 ) and G. Labrunie and J. Robert (J. Appl. Phys. 44 (1973), 4869 ).

The work of J. Robert and F. Clerc (SID 80 Digest Techn. Papers (1980), 30), J. Duchene (Displays 7 (1986), 3) and H. Schad (SID 82 Digest Techn. Papers (1982). , 244) have shown that liquid-crystalline phases must have high values for the ratio of the elastic constants K ₃ / K ₁ , high values for the optical anisotropy Δn and values for the dielectric anisotropy of Δε ≦ -0.5 in order to obtain highly informative display elements based on the ECB effect. On the ECB effect based electro-optical display elements have a homeotropic edge alignment (VA technology = V ertical A ligned). Even displays that use the so-called IPS or FFS effect, dielectric-negative liquid-crystal media can be used.

Displays using the ECB effect, have proved to be so-called VAN (V ertically A ligned N Ematic) See, for example, in the MVA (M Ultimatum D omain V ertical A lignment, including: Yoshide, H. et al., Lecture 3.1: "MVA LCD for Notebook or Mobile PCs ...", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 6-9 and Liu, CT et al., Lecture 15.1: "A 46-inch TFT-LCD HDTV Technology ...", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 750-753 ), PVA (Patterned Vertical Alignment, eg: Kim, Sang Soo, Lecture 15.4: "Super PVA Sets New State-of-the-Art for LCD TV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 760-763 ), ASV (Advanced Super View, eg: Shigeta, Mitzuhiro and Fukuoka, Hirofumi, Lecture 15.2: "Development of High Quality LCDTV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 754-757 ) Displays, besides IPS ( I n P lane S witching) (eg: Yeo, SD, Lecture 15.3: "A LC Display for the TV Application," SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 758 & 759 ) The long-known TN (T Wisted N Ematic) displays, as one of the top three at the time newer types of liquid crystal displays, in particular for television applications, established. In general terms, the technologies are eg in Souk, Jun, SIDSeminar 2004, Seminar M-6: "Recent Advances in LCD Technology", Seminar Lecture Notes, M-6/1 to M-6/26 and Miller, lan, SIDSeminar 2004, Seminar M-7: "LCD Television", Seminar Lecture Notes, M-7/1 to M-7/32 , compared. Although the switching times of modern ECB displays have already been significantly improved by overdrive control methods, eg: Kim, Hyeon Kyeong et al., Lecture 9.1: "A 57-in. Wide UXGA TFT-LCD for HDTV Application," SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 106-109 , the achievement of videotauglichen switching times, especially when switching grayscale, still a not yet satisfactorily solved problem.

For the technical application of this effect in electro-optical display elements FK phases are needed, which must meet a variety of requirements. Particularly important here are the chemical resistance to moisture, air and physical influences such as heat, radiation in the infrared, visible and ultraviolet range and electrical alternating and alternating fields.

Furthermore, technically usable LC phases require a liquid-crystalline mesophase in a suitable temperature range and a low viscosity.

In none of the previously known series of compounds with liquid-crystalline mesophase there is a single compound that meets all these requirements. As a rule, mixtures of two to 25, preferably three to 18, compounds are therefore prepared in order to obtain substances which can be used as LC phases. However, optimal phases could not easily be produced in this way since no liquid crystal materials with clearly negative dielectric anisotropy and sufficient long-term stability were available to date.

Matrix liquid crystal displays (MFK displays) are known. As non-linear elements for individual switching of the individual pixels, for example, active elements (ie transistors) can be used.

1. 1. MOS (Metal Oxide Semiconductor)-Transistoren auf Silizium-Wafer als Substrat.
2. 2. Dünnfilm-Transistoren (TFT) auf einer Glasplatte als Substrat.

One speaks then of an "active matrix", whereby one can distinguish two types:

1. 1. MOS (Metal Oxide Semiconductor) transistors on silicon wafer as a substrate.
2. 2. Thin-film transistors (TFT) on a glass plate as a substrate.

Type 1 typically uses dynamic scattering or guest-host effect as the electro-optic effect. The use of monocrystalline silicon as a substrate material limits the display size, since the modular composition of various partial displays on the joints leads to problems.

In the more promising type 2, which is preferred, the TN effect is usually used as the electro-optical effect.

A distinction is made between two technologies: TFTs made of compound semiconductors, such as e.g. CdSe or TFTs based on polycrystalline or amorphous silicon. The latter technology is being worked on worldwide with great intensity.

The TFT matrix is applied on the inside of one glass plate of the display, while the other glass plate on the inside carries the transparent counter electrode. Compared to the size of the pixel electrode, the TFT is very small and practically does not disturb the image. This technology can also be extended to fully color-capable image representations, wherein a mosaic of red, green and blue filters is arranged such that each one filter element is opposite to a switchable image element.

The term MFK displays here includes any matrix display with integrated nonlinear elements, ie in addition to the active matrix also displays with passive elements such as varistors or diodes (MIM = metal insulator metal).

Such MFK displays are particularly suitable for TV applications (eg pocket TV) or for high-information displays in automotive or aircraft. In addition to problems with regard to the angle dependence of the contrast and the switching times, difficulties arise in the case of MFK displays due to the insufficiently high specific resistance of the liquid-crystal mixtures [ TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, Sept. 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, p. 141 ff, par is; STROMER, M., Proc. Eurodisplay 84, Sept. 1984: Design of Thin Film Transistors for Matrix Liquid Crystal Displays, p. 145 ff, par is]. As the resistance decreases, the contrast of a MFK display degrades. Since the resistivity of the liquid crystal mixture, through interaction with the internal surfaces of the display, generally decreases over the lifetime of an MFK display, high (initial) resistance is very important for displays that must have acceptable resistance values over a long period of operation.

There is thus still a great need for MFK displays with very high resistivity combined with a large operating temperature range, short switching times and low threshold voltage, with the help of which different gray levels can be generated.

The drawback of the commonly used MFK TN displays is their relatively low contrast, the relatively high viewing angle dependence, and the difficulty in creating grayscale in these displays.

Significantly better viewing angle dependencies are found on VA displays and are therefore mainly used for TVs and monitors. However, there is still a need to improve the switching times, especially with regard to the use of television sets with "frame rates" (frame rate / repetition rates) of more than 60 Hz. However, the characteristics, such as the low-temperature stability, must not be impaired.

The invention is based on the object liquid crystal mixtures, such as known from DE 10 2012 004871 A1 . WO 2006/002747 A1 . DE 10 2004 012970 A1 . DE10 2011 013007 . EP 2 722 380 A2 and WO 200/017180 A1 in particular for monitor and TV applications which are based on the ECB or on the IPS or FFS effect to provide, which have the disadvantages mentioned above, or only to a lesser extent. In particular, it must be ensured for monitors and TVs that they operate at extremely high and extremely low temperatures and at the same time have very low switching times and at the same time have an improved reliability behavior, in particular no or significantly reduced image sticking after long runtimes. For example, at elevated temperatures, decomposition may occur within the liquid crystal mixture. Under UV exposure, a large decrease in Voltage Holding Ratio (VHR) is often observed.

Object of the present invention is therefore to provide liquid crystal mixtures that cause no or no significant problems at elevated temperatures and under UV exposure.

Surprisingly, it is possible to improve the reliability and thus the voltage holding ratio after UV exposure (Suntest) without adversely affecting the voltage holding ratio value when using compounds of the formula I-1 and / or I-2 in liquid-crystal mixtures. especially in LC blends with negative dielectric anisotropy, preferably for VA, IPS and FFS applications, most preferably for UB (ultra bright )FFS displays.

The invention thus relates to a liquid-crystalline medium according to claim 1, which contains the compound of formula I-1 and / or the compound of formula I-2.

The mixtures according to the invention are both stable at elevated temperatures and under UV exposure, preferably show very broad nematic phase ranges with clearing points ≥ 70 ° C, preferably ≥ 75 ° C, in particular ≥ 80 ° C, very favorable values for the capacitive threshold, relative high values for the holding ratio and at the same time very good low-temperature stabilities at -20 ° C and -30 ° C as well as very low Rotational viscosities and low switching times. The mixtures according to the invention are further distinguished by the fact that, in addition to the improvement of the rotational viscosity γ ₁ , relatively high values of the elastic constants K ₃₃ can be observed to improve the switching times.

Some preferred embodiments of the mixtures according to the invention are mentioned below.

Preferably, either the compound of the formula I-1 or the compound of the formula I-2 is added to the liquid-crystalline mixture. The compound I-1 or I-2 is used in amounts of 50-10,000 ppm, in particular 100-6,000 ppm and very particularly preferably 300-4,000 ppm, based on the liquid-crystalline mixture. If the liquid-crystal mixture contains the compounds I-1 and I-2, the two compounds may be added in equal amounts or in different amounts. However, the total concentration should not exceed 6000 - 10000 ppm based on the mixture.

The compounds of formulas I-1 and I-2 are commercially available, e.g. B. from the company Sigma-Aldrich.

1. a) Flüssigkristallines Medium, welches eine oder mehrere Verbindungen ausgewählt aus der Gruppe der Verbindungen der Formeln IIA, IIB und IIC enthält,
   
   
   
   worin

   R^2A, R^2B und R^2C

   jeweils unabhängig voneinander H, einen unsubstituierten, einen einfach durch CN oder CF₃ oder mindestens einfach durch Halogen substituierten Alkyl- oder Alkenylrest mit bis zu 15 C-Atomen, wobei in diesen Resten auch eine oder mehrere CH₂-Gruppen durch -O-, -S-,

   

   -C≡C-, -CF₂O-, -OCF₂-, -OC-O- oder -O-CO- so ersetzt sein können, dass O-Atome nicht direkt miteinander verknüpft sind, vorzugsweise Alkyl oder Alkenyl mit jeweils 1 bzw. 2-6 C-Atomen,

   L^1-4

   jeweils unabhängig voneinander F, Cl, CF₃ oder CHF₂, vorzugsweise F,

   Z² und Z^2'

   jeweils unabhängig voneinander Einfachbindung, -CH₂CH₂-, -CH=CH-, -CF₂O-, -OCF₂-, -CH₂O-, -OCH₂-, -COO-, -OCO-, -C₂F₄-, -CF=CF-, -CH=CHCH₂O-, vorzugsweise eine Einfachbindung, -OCH₂- oder -CH₂CH₂-,

   p

   0, 1 oder 2,

   q

   0 oder 1, und

   v

   1 bis 6

   bedeuten.

Preferred embodiments of the liquid-crystalline medium according to the invention are given below:

1. a) liquid-crystalline medium which contains one or more compounds selected from the group of the compounds of the formulas IIA, IIB and IIC,
   
   
   
   wherein

   R ^2A , R ^2B and R ^2C

   in each case independently of one another H, an unsubstituted alkyl or alkenyl radical having up to 15 carbon atoms which is monosubstituted by CN or CF ₃ or at least monosubstituted by halogen, where one or more CH ₂ groups in these radicals are also represented by -O-, -S-,

   

   -C≡C, -CF ₂ O-, -OCF ₂ -, -OC-O- or -O-CO- can be replaced so that O atoms are not directly linked, preferably alkyl or alkenyl, each with 1 or 2-6 C atoms,

   L ^1-4

   each independently of one another F, Cl, CF ₃ or CHF ₂ , preferably F,

   Z ² and Z ^{2 '}

   each independently represents single bond, -CH ₂ CH ₂ -, -CH = CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF = CF-, -CH = CHCH ₂ O-, preferably a single bond, -OCH ₂ - or -CH ₂ CH ₂ -,

   p

   0, 1 or 2,

   q

   0 or 1, and

   v

   1 to 6

   mean.

In the compounds of formulas IIA and IIB, Z ^{2 may have the} same or different meanings. In the compounds of the formula IIB, Z ² and Z ^{2 'may have the} same or different meanings.

In the compounds of the formulas IIA, IIB and IIC, R ^2A , R ^2B and R ^{2C are} each preferably alkyl or alkenyl having 1 or ₂ to 6 carbon atoms, in particular CH ₃ , C ₂ H ₅ , nC ₃ H ₇ , nC ₄ H ₉ , nC ₅ H _11. , CH ₂ = CH,

In the compounds of the formulas IIA and IIB, L ¹ , L ² , L ³ and L ^{4 are} preferably L ¹ = L ² = F and L ³ = L ⁴ = F, furthermore L ¹ = F and L ² = Cl, L ¹ = Cl and L ² = F, L ³ = F and L ⁴ = Cl, L ³ = Cl and L ⁴ = F. Z ² and Z ^{2 '} in the formulas IIA and IIB preferably each independently a single bond, further a -C ₂ H ₄ - or a -CH ₂ O bridge.

If in the formula IIB Z ² = -C ₂ H ₄ - or -CH ₂ O-, Z ^{2 'is} preferably a single bond or if Z ^2' = -C ₂ H ₄ - or -CH ₂ O-, Z ^{2 is} preferably a single bond. In the compounds of the formulas IIA and IIB, (O) C _v H _{2v + 1} preferably denotes OC _v H _{2v + 1} , furthermore C _v H _{2v + 1} . In the compounds of the formula IIC, (O) C _v H _{2v + 1 is} preferably C _v H _{2v + 1} . In the compounds of the formula IIC, L ³ and L ^{4 are} preferably in each case F.

worin Alkyl und Alkyl* jeweils unabhängig voneinander einen geradkettigen Alkylrest mit 1-6 C-Atomen bedeuten.Preferred compounds of the formulas IIA, IIB and IIC are mentioned below:

wherein alkyl and alkyl * each independently represent a straight-chain alkyl radical having 1-6 C atoms.

Particularly preferred mixtures according to the invention contain one or more compounds of the formulas IIA-2, IIA-8, IIA-14, IIA-26, II-28, IIA-33, IIA-39, IIA-45, IIA-46, IIA-47 , IIA-50, IIB-2, IIB-11, IIB-16 and IIC-1.

The proportion of compounds of the formulas IIA and / or IIB in the total mixture is preferably at least 20% by weight.

worin Alkyl und Alkyl*' die oben angegebenen Bedeutungen haben, vorzugsweise in Mengen von > 3 Gew.%, insbesondere > 5 Gew.% und besonders bevorzugt von 5-25 Gew.%.

• b) Flüssigkristallines Medium, welches zusätzlich eine oder mehrere Verbindungen der Formel III
  
  enthält,
  worin

  R³¹ und R³²

  jeweils unabhängig voneinander einen geradkettigen Alkyl-, Alkoxy, Alkenly-, Alkoxyalkyl- oder Alkoxyrest mit bis zu 12 C-Atomen, und

  

  

  Z³

  Einfachbindung, -CH₂CH₂-, -CH=CH-, -CF₂O-, -OCF₂-, -CH₂O-, -OCH₂-, -COO-, -OCO-, -C₂F₄-, -C₄H₈-, -CF=CF-

  bedeuten.
  Bevorzugte Verbindungen der Formel III werden nachfolgend genannt,
  
  
  
  
  worin

  Alkyl und Alkyl*

  jeweils unabhängig voneinander einen geradkettigen Alkylrest mit 1-6 C-Atomen

  bedeuten.
  Vorzugsweise enthält das erfindungsgemäße Medium mindestens eine Verbindung der Formel IIIa und/oder Formel IIIb.
  Der Anteil an Verbindungen der Formel III im Gesamtgemisch beträgt vorzugsweise mindestens 5 Gew.%.
• c) Flüssigkristallines Medium enthaltend zusätzlich eine Verbindung der Formel
  
  und / oder
  
  und / oder
  
  vorzugsweise in Gesamtmengen von ≥ 5 Gew.%, insbesondere von ≥ 10 Gew.%.
  Weiterhin bevorzugt sind erfindungsgemäße Mischungen enthaltend die Verbindung der Formel (Acronym: CC-3-V1)
  
  vorzugsweise in Mengen von 2-15 %.
  Bevorzugte Mischungen enthalten 5-60 %, vorzugsweise 10-55 %, insbesondere 20-50 Gew.% der Verbindung der Formel (Acronym: CC-3-V)
  
  
  Weiterhin bevorzugt sind Mischungen, die eine Verbindung der Formel (Acronym: CC-3-V)
  
  und eine Verbindung der Formel (Acronym: CC-3-V1)
  
  enthalten, vorzugsweise in Mengen von 10 - 60 %.
• d) Flüssigkristallines Medium, welches zusätzlich eine oder mehrere Vierkernverbindungen der Formeln,
  
  
  
  
  
  
  
  
  
  worin

  R^7-10

  jeweils unabhängig voneinander eine der in Anspruch 3 für R^2A angegebenen Bedeutung haben, und

  w und x

  jeweils unabhängig voneinander 1 bis 6,

  bedeuten,
  enthält.
  Insbesondere bevorzugt sind Mischungen enthaltend mindestens eine Verbindung der Formel V-9.
• e) Flüssigkristallines Medium, welches zusätzlich eine oder mehrere Verbindungen der Formeln Y-1 bis Y-6,
  
  
  
  
  
  
  enthält,
  worin R¹⁴-R¹⁹ jeweils unabhängig voneinander einen Alkyl- oder Alkoxyrest mit 1-6 C-Atomen bedeuten; z und m bedeuten jeweils unabhängig voneinander 1-6; x bedeutet 0, 1, 2 oder 3.
  Insbesondere bevorzugt enthält das erfindungsgemäße Medium eine oder mehrere Verbindungen der Formel Y-1 bis Y-6, vorzugsweise in Mengen von ≥ 5 Gew.%.
• f) Flüssigkristallines Medium enthaltend zusätzlich ein oder mehrere fluorierte Terphenyle der Formeln T-1 bis T-21,
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  worin
  R geradkettiger Alkyl- oder Alkoxyrest mit 1-7 C-Atomen bedeutet, und m = 0, 1, 2, 3, 4, 5 oder 6 und n 0, 1, 2, 3 oder 4 bedeuten,
  enthält.
  Vorzugsweise bedeutet R Methyl, Ethyl, Propyl, Butyl, Pentyl, Hexyl Methoxy, Ethoxy, Propoxy, Butoxy, Pentoxy.
  Das erfindungsgemäße Medium enthält ein oder mehrere Terphenyle der Formeln T-1 bis T-21 vorzugsweise in Mengen von 2-30 Gew.%, insbesondere von 5-20 Gew.%.
  Besonders bevorzugt sind Verbindungen der Formeln T-1, T-2, T-4, T-20 und T-21. In diesen Verbindungen bedeutet R vorzugsweise Alkyl, ferner Alkoxy jeweils mit 1-5 C-Atomen. In den Verbindungen der Formel T-20 bedeutet R vorzugsweise Alkyl oder Alkenyl, insbesondere Alkyl. In der Verbindung der Formel T-21 bedeutet R vorzugsweise Alkyl.
  Vorzugsweise werden die Terphenyle in den erfindungsgemäßen Mischungen eingesetzt, wenn der Δn-Wert der Mischung ≥ 0,1 sein soll. Bevorzugte Mischungen enthalten 2-20 Gew.% einer oder mehrerer Terphenyl-Verbindungen ausgewählt aus der Gruppe der Verbindungen T-1 bis T-21.
• g) Flüssigkristallines Medium enthaltend zusätzlich ein oder mehrere Biphenyle der Formeln B-1 bis B-3,
  
  
  
  worin

  Alkyl und Alkyl*

  jeweils unabhängig voneinander einen geradkettigen Alkylrest mit 1-6 C-Atomen, und

  Alkenyl und Alkenyl*

  jeweils unabhängig voneinander einen geradkettigen Alkenylrest mit 2-6 C-Atomen

  bedeuten.
  Der Anteil der Biphenyle der Formeln B-1 bis B-3 in der Gesamtmischung beträgt vorzugsweise mindestens 3 Gew.%, insbesondere ≥ 5 Gew.%.
  Von den Verbindungen der Formeln B-1 bis B-3 sind die Verbindungen der Formel B-2 insbesondere bevorzugt.
  Besonders bevorzugte Biphenyle sind
  
  
  
  
  worin Alkyl* einen Alkylrest mit 1-6 C-Atomen bedeutet. Insbesondere bevorzugt enthält das erfindungsgemäße Medium eine oder mehrere Verbindungen der Formeln B-1a und/oder B-2c.
• h) Flüssigkristallines Medium enthaltend mindestens eine Verbindung der Formeln Z-1 bis Z-7,
  
  
  
  
  
  
  
  
  
  worin R und Alkyl die oben angegebenen Bedeutungen haben.
• i) Flüssigkristallines Medium enthaltend mindestens eine Verbindung der Formeln O-1 bis 0-18,
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  worin R¹ und R² die für R^2A angegebenen Bedeutungen haben. Vorzugsweise bedeuten R¹ und R² jeweils unabhängig voneinander geradkettiges Alkyl oder Alkenyl.

Particularly preferred media according to the invention comprise at least one compound of the formula IIC-1,

wherein alkyl and alkyl * 'have the meanings given above, preferably in amounts of> 3% by weight, in particular> 5% by weight and particularly preferably from 5 to 25% by weight.

• b) liquid-crystalline medium which additionally contains one or more compounds of the formula III
  
  contains
  wherein

  ^R31 and ^R32

  each independently of one another a straight-chain alkyl, alkoxy, alkenyl, alkoxyalkyl or alkoxy radical having up to 12 C atoms, and

  

  

  Z ³

  Single bond, -CH ₂ CH ₂ -, -CH = CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -C ₄ H ₈ -, -CF = CF-

  mean.
  Preferred compounds of the formula III are mentioned below,
  
  
  
  
  wherein

  Alkyl and alkyl *

  each independently a straight-chain alkyl radical having 1-6 C atoms

  mean.
  The medium according to the invention preferably comprises at least one compound of the formula IIIa and / or formula IIIb.
  The proportion of compounds of the formula III in the total mixture is preferably at least 5% by weight.
• c) Liquid-crystalline medium additionally containing a compound of the formula
  
  and or
  
  and or
  
  preferably in total amounts of ≥ 5% by weight, in particular of ≥ 10% by weight.
  Preference is furthermore given to mixtures according to the invention comprising the compound of the formula (acronym: CC-3-V1)
  
  preferably in amounts of 2-15%.
  Preferred mixtures contain 5-60%, preferably 10-55%, in particular 20-50% by weight of the compound of the formula (acronym: CC-3-V)
  
  
  Preference is furthermore given to mixtures which comprise a compound of the formula (acronym: CC-3-V)
  
  and a compound of the formula (acronym: CC-3-V1)
  
  contained, preferably in amounts of 10 - 60%.
• d) liquid-crystalline medium which additionally contains one or more four-nucleus compounds of the formulas,
  
  
  
  
  
  
  
  
  
  wherein

  R ^7-10

  each independently of one another have one of the meaning given in claim 3 for R ^2A , and

  w and x

  each independently from 1 to 6,

  mean,
  contains.
  Particular preference is given to mixtures comprising at least one compound of the formula V-9.
• e) liquid-crystalline medium which additionally contains one or more compounds of the formulas Y-1 to Y-6,
  
  
  
  
  
  
  contains
  wherein R ¹⁴ -R ¹⁹ each independently represent an alkyl or alkoxy radical having 1-6 C atoms; z and m are each independently 1-6; x is 0, 1, 2 or 3.
  With particular preference, the medium according to the invention contains one or more compounds of the formula Y-1 to Y-6, preferably in amounts of ≥ 5% by weight.
• f) liquid-crystalline medium additionally containing one or more fluorinated terphenyls of the formulas T-1 to T-21,
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  wherein
  R is straight-chain alkyl or alkoxy radical having 1-7 C atoms, and m is 0, 1, 2, 3, 4, 5 or 6 and n is 0, 1, 2, 3 or 4,
  contains.
  Preferably R is methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentoxy.
  The medium according to the invention contains one or more terphenyls of the formulas T-1 to T-21, preferably in amounts of from 2 to 30% by weight, in particular from 5 to 20% by weight.
  Particular preference is given to compounds of the formulas T-1, T-2, T-4, T-20 and T-21. In these compounds R preferably denotes alkyl, furthermore alkoxy in each case with 1-5 C atoms. In the compounds of the formula T-20, R preferably denotes alkyl or alkenyl, in particular alkyl. In the compound of formula T-21, R is preferably alkyl.
  The terphenyls are preferably used in the mixtures according to the invention if the Δn value of the mixture is to be ≥ 0.1. Preferred mixtures contain 2-20% by weight of one or more terphenyl compounds selected from the group of compounds T-1 to T-21.
• g) liquid-crystalline medium additionally containing one or more biphenyls of the formulas B-1 to B-3,
  
  
  
  wherein

  Alkyl and alkyl *

  each independently of one another a straight-chain alkyl radical having 1-6 C atoms, and

  Alkenyl and alkenyl *

  each independently a straight-chain alkenyl radical having 2-6 C atoms

  mean.
  The proportion of biphenyls of the formulas B-1 to B-3 in the overall mixture is preferably at least 3% by weight, in particular ≥ 5% by weight.
  Of the compounds of the formulas B-1 to B-3, the compounds of the formula B-2 are particularly preferred.
  Particularly preferred biphenyls are
  
  
  
  
  wherein alkyl * is an alkyl radical having 1-6 C atoms. With particular preference, the medium according to the invention contains one or more compounds of the formulas B-1a and / or B-2c.
• h) liquid-crystalline medium containing at least one compound of the formulas Z-1 to Z-7,
  
  
  
  
  
  
  
  
  
  wherein R and alkyl have the meanings given above.
• i) liquid-crystalline medium containing at least one compound of the formulas O-1 to 0-18,
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  wherein R ¹ and R ^{2 have} the meanings given for R ^2A . Preferably, R ¹ and R ^{2 are} each independently straight-chain alkyl or alkenyl.

Preferred media contain one or more compounds of formulas O-1, O-3, O-4, O-6, O-7, O-10, O-11, O-12, O-14, O-15, O -16 and / or 0-17.

Very particular preference is given to mixtures according to the invention containing the compounds of the formula O-10, O-12, O-16 and / or O-17, in particular in amounts of 5-30%.

Preferred compounds of the formulas O-10 and 0-17 are mentioned below:

The medium according to the invention particularly preferably contains the trinuclear compounds of the formula O-10a and / or of the formula O-10b in combination with one or more dinuclear compounds of the formulas O-17a to O-17d. Preferably, the total amount of the compounds of formula O-10a and / or O-10b in combination with one or more compounds selected from the binuclear compounds of the formulas O-17a to O-17d 5-40%, most preferably 15-35%.

Very particularly preferred mixtures contain the compounds O-10a and O-17a:

The compounds O-10a and O-17a are preferably present in the mixture in a concentration of 15-35%, particularly preferably 15-25% and particularly preferably 18-22%, based on the total mixture.

Very particularly preferred mixtures contain the compounds O-10b and O-17a:

The compounds O-10b and O-17a are preferably present in the mixture in a concentration of 15-35%, particularly preferably 15-25% and particularly preferably 18-22%, based on the total mixture.

Very particularly preferred mixtures contain the following three compounds:

The compounds O-10a, O-10b and O-17a are preferably present in the mixture in a concentration of 15-35%, particularly preferably 15-25% and particularly preferably 18-22%, based on the total mixture.

worin R¹ und R² die oben angegegebenen Bedeutungen haben. Vorzugsweise bedeutet in den Verbindungen 0-6, 0-7 und O-17 R¹ Alkyl oder Alkenyl mit 1-6 bzw. 2-6 C-Atomen und R² Alkenyl mit 2-6 C-Atomen.Preferred mixtures contain at least one compound selected from the group of compounds

wherein R ¹ and R ^{2 have} the meanings given above. In the compounds 0-6, 0-7 and O-17, R ¹ preferably denotes alkyl or alkenyl having 1-6 or 2-6 C atoms and R ² alkenyl having 2-6 C atoms.

worin Alkyl einen Alkylrest mit 1-6 C-Atomen bedeutet. Vorzugsweise sind die Verbindungen der Formel O-6, O-7 und O-17e-h in den erfindungsgemäßen Mischungen mit 1 - 40 Gew.%, vorzugsweise 2 - 35 Gew.% und ganz besonders bevorzugt 2 - 30 Gew.% enthalten.

• j) Bevorzugte erfindungsgemäße flüssigkristalline Medien enthalten eine oder mehrere Substanzen, die eine Tetrahydronaphthyl- oder Naphthyl-Einheit aufweisen, wie z.B. die Verbindungen der Formeln N-1 bis N-5,
  
  
  
  
  
  • worin R^1N und R^2N jeweils unabhängig voneinander die für R^2A angegebenen Bedeutungen haben, vorzugsweise geradkettiges Alkyl, geradkettiges Alkoxy oder geradkettiges Alkenyl bedeuten, und
  • Z¹ und Z² jeweils unabhängig voneinander -C₂H₄-, -CH=CH-, -(CH₂)₄-, -(CH₂)₃O-, -O(CH₂)₃-, -CH=CHCH₂CH₂-, -CH₂CH₂CH=CH-, -CH₂O-, -OCH₂-, -COO-, -OCO-, -C₂F₄-, -CF=CF-, -CF=CH-, -CH=CF-, -CF₂O-, -OCF₂-, -CH₂- oder eine Einfachbindung
  bedeuten.
• k) Bevorzugte Mischungen enthalten eine oder mehrere Verbindungen ausgewählt aus der Gruppe der Difluordibenzochroman-Verbindungen der Formel BC, Chromane der Formeln CR, fluorierte Phenanthrene der Formeln PH-1 und PH-2, fluorierte Dibenzofurane der Formeln BF-1 und BF-2,
  
  
  
  
  
  
  worin
  R^B1, R^B2, R^CR1, R^CR2, R¹, R² jeweils unabhängig voneinander die Bedeutung von R^2A aufweisen. c bedeutet 0, 1 oder 2. d bedeutet 1 oder 2. R¹ und R² bedeuten vorzugsweise unabhängig voneinander Alkyl oder Alkoxy mit 1 bis 6 C-Atomen.

Preferred mixtures contain at least one compound selected from the group of the compounds of the formulas O-6a, O-6b O-7a, O-7b, O-17e, O-17f, O-17g and O-17h:

wherein alkyl is an alkyl radical having 1-6 C atoms. The compounds of the formula O-6, O-7 and O-17e-h are preferably present in the mixtures according to the invention with 1-40% by weight, preferably 2-35% by weight and very particularly preferably 2-30% by weight.

• j) Preferred liquid-crystalline media according to the invention contain one or more substances which have a tetrahydronaphthyl or naphthyl unit, for example the compounds of the formulas N-1 to N-5,
  
  
  
  
  
  • wherein R ^1N and R ^2N each independently of one another have the meanings given for R ^2A , preferably straight-chain alkyl, straight-chain alkoxy or straight-chain alkenyl, and
  • Each of Z ¹ and Z ² is independently -C ₂ H ₄ -, -CH = CH-, - (CH ₂ ) ₄ -, - (CH ₂ ) ₃ O-, -O (CH ₂ ) ₃ -, -CH = CHCH ₂ CH ₂ -, -CH ₂ CH ₂ CH = CH-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF = CF-, -CF = CH-, -CH = CF-, -CF ₂ O-, -OCF ₂ -, -CH ₂ - or a single bond
  mean.
• k) Preferred mixtures contain one or more compounds selected from the group of difluorodibenzochroman compounds of the formula BC, chromans of the formulas CR, fluorinated phenanthrenes of the formulas PH-1 and PH-2, fluorinated dibenzofurans of the formulas BF-1 and BF-2,
  
  
  
  
  
  
  wherein
  R ^B1 , R ^B2 , ^CR1 R, R ^CR2 , R ¹ , R ² each independently have the meaning of R ^2A . c is 0, 1 or 2. d is 1 or 2. R ¹ and R ^{2 are} preferably independently of one another alkyl or alkoxy having 1 to 6 C atoms.

The mixtures according to the invention preferably contain the compounds of the formulas BC, CR, PH-1, PH-2 and / or BF in amounts of from 3 to 20% by weight, in particular in amounts of from 3 to 15% by weight.

worin

Alkyl und Alkyl*

jeweils unabhängig voneinander einen geradkettigen Alkylrest mit 1-6 C-Atomen, und

Alkenyl und Alkenyl*

jeweils unabhängig voneinander einen geradkettigen Alkenylrest mit 2-6 C-Atomen,

bedeuten.Particularly preferred compounds of the formulas BC, CR and BF are the compounds BC-1 to BC-7, CR-1 to CR-5, BF-1a to BF-1c,

wherein

Alkyl and alkyl *

each independently of one another a straight-chain alkyl radical having 1-6 C atoms, and

Alkenyl and alkenyl *

each independently of one another a straight-chain alkenyl radical having 2-6 C atoms,

mean.

• I) Bevorzugte Mischungen enthalten eine oder mehrere Indan-Verbindungen der Formeln In,
  
  worin

  R¹¹, R¹², R¹³

  jeweils unabhängig voneinander einen geradkettigen Alkyl-, Alkoxy-, Alkoxyalkyl- oder Alkenylrest mit 1-6 C-Atomen,

  R¹² und R¹³

  zusätzlich Halogen, vorzugsweise F,

  

  i

  0, 1 oder 2

  bedeuten.
  Bevorzugte Verbindungen der Formel In sind die nachfolgend genannten Verbindungen der Formeln In-1 bis In-16,
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  Besonders bevorzugt sind die Verbindungen der Formeln In-1, In-2, In-3 und In-4.
  Die Verbindungen der Formeln In und der Unterformeln In-1 bis In-16 werden vorzugsweise in Konzentrationen ≥ 5 Gew.%, insbesondere 5 - 30 Gew.% und ganz besonders bevorzugt 5 - 25 Gew.% in den erfindungsgemäßen Mischungen eingesetzt.
• m) Bevorzugte Mischungen enthalten zusätzlich eine oder mehrere Verbindungen der Formeln L-1 bis L-11,
  
  
  
  
  
  
  
  
  
  
  
  worin
  R, R¹ und R² jeweils unabhängig voneinander die für R^2A in Anspruch 5 angegebenen Bedeutungen haben und Alkyl ein Alkylrest mit 1-6 C-Atomen bedeutet. s bedeutet 1 oder 2.

Very particular preference is given to mixtures comprising one, two or three compounds of the formula BC-2, BF-1 and / or BF-2.

• I) Preferred mixtures contain one or more indane compounds of the formulas In,
  
  wherein

  R ¹¹ , R ¹² , R ¹³

  each independently of one another a straight-chain alkyl, alkoxy, alkoxyalkyl or alkenyl radical having 1-6 C atoms,

  R ¹² and R ¹³

  additionally halogen, preferably F,

  

  i

  0, 1 or 2

  mean.
  Preferred compounds of the formula In are the following compounds of the formulas In-1 to In-16,
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  Particularly preferred are the compounds of the formulas In-1, In-2, In-3 and In-4.
  The compounds of the formulas In and the sub-formulas In-1 to In-16 are preferably used in concentrations of at least 5% by weight, in particular from 5 to 30% by weight and very particularly preferably from 5 to 25% by weight, in the mixtures according to the invention.
• m) Preferred mixtures additionally contain one or more compounds of the formulas L-1 to L-11,
  
  
  
  
  
  
  
  
  
  
  
  wherein
  R, R ¹ and R ² each independently of one another have the meanings given for R ^2A in claim 5 and alkyl is an alkyl radical having 1-6 C atoms. s means 1 or 2.

Particular preference is given to the compounds of the formulas L-1 and L-4, in particular L-4.

The compounds of the formulas L-1 to L-11 are preferably used in concentrations of 5 to 50% by weight, in particular 5 to 40% by weight and very particularly preferably 10 to 40% by weight.

Particularly preferred mixture concepts are mentioned below: (The acronyms used are explained in Table A. n and m here in each case independently of one another denote 1-15, preferably 1-6.)

• CPY-n-Om, insbesondere CPY-2-O2, CPY-3-O2 und/oder CPY-5-02, vorzugsweise in Konzentrationen > 5 %, insbesondere 10-30 %, bezogen auf die Gesamtmischung,
  und/oder
• CY-n-Om, vorzugsweise CY-3-O2, CY-3-O4, CY-5-O2 und/oder CY-5-04, vorzugsweise in Konzentrationen > 5 %, insbesondere 15-50 %, bezogen auf die Gesamtmischung,
  und/oder
• CCY-n-Om, vorzugsweise CCY-4-O2, CCY-3-O2, CCY-3-O3, CCY-3-01 und/oder CCY-5-O2, vorzugsweise in Konzentrationen > 5 %, insbesondere 10-30 %, bezogen auf die Gesamtmischung,
  und/oder
• CLY-n-Om, vorzugsweise CLY-2-O4, CLY-3-O2 und/oder CLY-3-O3, vorzugsweise in Konzentrationen > 5 %, insbesondere 10-30 %, bezogen auf die Gesamtmischung,
  und/oder
• CK-n-F, vorzugsweise CK-3-F, CK-4-F und/oder CK-5-F, vorzugsweise > 5 %, insbesondere 5-25 %, bezogen auf die Gesamtmischung.

The mixtures according to the invention preferably contain

• CPY-n-Om, in particular CPY-2-O2, CPY-3-O2 and / or CPY-5-02, preferably in concentrations of> 5%, in particular 10-30%, based on the total mixture,
  and or
• CY-n-Om, preferably CY-3-O2, CY-3-O4, CY-5-O2 and / or CY-5-04, preferably in concentrations> 5%, in particular 15-50%, based on the total mixture .
  and or
• CCY-n-Om, preferably CCY-4-O2, CCY-3-O2, CCY-3-O3, CCY-3-01 and / or CCY-5-O2, preferably in concentrations> 5%, in particular 10-30 %, based on the total mixture,
  and or
• CLY-n-Om, preferably CLY-2-O4, CLY-3-O2 and / or CLY-3-O3, preferably in concentrations> 5%, in particular 10-30%, based on the total mixture,
  and or
• CK-nF, preferably CK-3-F, CK-4-F and / or CK-5-F, preferably> 5%, in particular 5-25%, based on the total mixture.

• CPY-n-Om und CY-n-Om, vorzugsweise in Konzentrationen von 10-80 % bezogen auf die Gesamtmischung,
  und/oder
• CPY-n-Om und CK-n-F, vorzugsweise in Konzentrationen von 10-70 % bezogen auf die Gesamtmischung,
  und/oder
• CPY-n-Om und PY-n-Om, vorzugsweise CPY-2-02 und/oder CPY-3-02 und PY-3-O2, vorzugsweise in Konzentrationen von 10 - 45 % bezogen auf die Gesamtmischung,
  und/oder
• CPY-n-Om und CLY-n-Om, vorzugsweise in Konzentrationen von 10-80 % bezogen auf die Gesamtmischung.
  und/oder
• CCVC-n-V, vorzugsweise CCVC-3-V, vorzugsweise in Konzentrationen von 2 - 10 % bezogen auf die Gesamtmischung,
  und/oder
• CCC-n-V, vorzugsweise CCC-2-V und/oder CCC-3-V, vorzugsweise in Konzentrationen von 2 - 10 % bezogen auf die Gesamtmischung,
  und/oder
• CC-V-V oder CC-V-V1, vorzugsweise in Konzentrationen von 5 - 50 % bezogen auf die Gesamtmischung.

Preference is furthermore given to mixtures according to the invention which contain the following mixture concepts:
(n and m are each independently 1-6.)

• CPY-n-Om and CY-n-Om, preferably in concentrations of 10-80% based on the total mixture,
  and or
• CPY-n-Om and CK-nF, preferably in concentrations of 10-70% based on the total mixture,
  and or
• CPY-n-Om and PY-n-Om, preferably CPY-2-02 and / or CPY-3-02 and PY-3-O2, preferably in concentrations of 10-45% based on the total mixture,
  and or
• CPY-n-Om and CLY-n-Om, preferably in concentrations of 10-80% based on the total mixture.
  and or
• CCVC-nV, preferably CCVC-3-V, preferably in concentrations of 2-10% based on the total mixture,
  and or
• CCC-nV, preferably CCC-2-V and / or CCC-3-V, preferably in concentrations of 2-10% based on the total mixture,
  and or
• CC-VV or CC-V-V1, preferably in concentrations of 5 - 50% based on the total mixture.

Another object of the invention is an electro-optical display with an active matrix addressing based on the ECB, VA, PS-VA, PA-VA, IPS, PS-IPS, FFS, UB-FFS or PS -FFS effect, characterized in that it contains as a dielectric liquid-crystalline medium according to one or more of claims 1 to 15.

The liquid-crystalline medium according to the invention preferably has a nematic phase of ≤ -20 ° C to ≥ 70 ° C, more preferably from ≤ -30 ° C to ≥ 80 ° C, most preferably from ≤ -40 ° C to ≥ 90 ° C ,

In this case, the term "having a nematic phase" on the one hand means that no smectic phase and no crystallization is observed at low temperatures at the corresponding temperature and, on the other hand, that no clarification occurs during heating from the nematic phase. The investigation at low temperatures is carried out in a flow viscometer at the appropriate temperature and by storage in test cells corresponding to the electro-optical application Layer thickness checked for at least 100 hours. When the storage stability at a temperature of -20 ° C in a corresponding test cell is 1,000 hours or more, the medium is said to be stable at this temperature. At temperatures of -30 ° C or -40 ° C the corresponding times are 500 h or 250 h. At high temperatures, the clearing point is measured in capillaries by conventional methods.

The liquid-crystal mixture preferably has a nematic phase range of at least 60 K and a flow viscosity v ₂₀ of at most 30 mm ² · s ^-1 at 20 ° C.

The values of the birefringence Δn in the liquid-crystal mixture are generally between 0.07 and 0.16, preferably between 0.08 and 0.13.

The liquid-crystal mixture according to the invention has a Δ∈ of -0.5 to -8.0, in particular of -2.5 to -6.0, where Δ∈ denotes the dielectric anisotropy. The rotational viscosity γ ₁ at 20 ° C is preferably ≤ 150 mPa · s, especially ≤ 120 mPa · s.

The liquid-crystal media according to the invention have relatively small values for the threshold voltage (Vo). Preferably, they are in the range of 1.7V to 3.0V, more preferably ≤ 2.5V, and most preferably ≤ 2.3V.

The term "threshold voltage" for the present invention refers to the capacitive threshold (V ₀ ), also called Freedericksz threshold, unless explicitly stated otherwise.

In addition, the liquid-crystal media according to the invention have high values for the voltage holding ratio in liquid-crystal cells.

As a rule, liquid crystal media with a low drive voltage or threshold voltage show a lower voltage holding ratio than those with a larger drive voltage or threshold voltage and vice versa.

For the present invention, the terms "dielectrically positive compounds" mean those compounds with a Δε> 1.5, "dielectrically neutral compounds" those with -1.5 ≦ Δε ≦ 1.5 and "dielectrically negative" compounds those with Δε <- 1.5. Here, the dielectric anisotropy of the compounds is determined by 10% of the compounds are dissolved in a liquid crystalline host and the capacity of the resulting mixture in at least one test cell with 20 micron layer thickness is determined with homeotropic and homogeneous surface orientation at 1 kHz. The measurement voltage is typically 0.5 V to 1.0 V, but it is always lower than the capacitive threshold of the liquid crystal mixture under investigation.

All reported temperatures for the present invention are in ° C.

The mixtures according to the invention are suitable for all VA-TFT applications, such as, for example, VAN, MVA, (S) -PVA, ASV, PSA (polymer-sustained VA) and PS-VA (polymer-stabilized VA). Furthermore, they are for IPS (I n p lane s witching) and FFS (F rings f ield s witching), preferably UB-FFS, with a negative Δε suitable.

The nematic liquid-crystal mixtures in the displays according to the invention generally contain two components A and B, which in turn consist of one or more individual compounds.

The component A has a markedly negative dielectric anisotropy and gives the nematic phase a dielectric anisotropy of ≦ -0.5. It preferably contains, in addition to one or more compounds of the formulas IIA, IIB and / or IIC, furthermore one or more compounds of the formula 0-17.

The proportion of component A is preferably between 45 and 100%, in particular between 60 and 100%.

For component A, one (or more) individual compound (s) is preferably selected which have a value of Δε ≦ -0.8. This value must be the more negative the smaller the proportion A of the total mixture is.

The component B has a pronounced nematogeneity and a flow viscosity of not more than 30 mm ² .s ^-1 , preferably not more than 25 mm ² .s ^-1 , at 20 ° C.

The skilled worker is known from the literature a variety of suitable materials. Particular preference is given to compounds of the formulas 0-17.

Particularly preferred individual compounds of component B are extremely low-viscosity nematic liquid crystals having a flow viscosity of not more than 18, preferably not more than 12 mm ² · s ¹ , at 20 ° C.

Component B is monotropic or enantiotropic nematic, has no smectic phases and can prevent the occurrence of smectic phases in liquid crystal mixtures up to very low temperatures. If, for example, a smectic liquid-crystal mixture is mixed with in each case different materials with high nematogeneity, the degree of suppression of smectic phases achieved can be used to compare the nematogeneity of these materials.

Optionally, the mixture may also contain a component C, which are compounds having a dielectric anisotropy of Δε ≥ 1.5. These so-called positive compounds are generally contained in a mixture with negative dielectric anisotropy in amounts of ≦ 20% by weight, based on the total mixture.

worin

R

geradkettiges Alkyl, Alkoxy oder Alkenyl mit jeweils 1 bzw. 2 bis 6 C-Atomen, und

X

F, Cl, CF₃, OCF₃, OCHFCF₃ oder CCF₂CHFCF₃, vorzugsweise F oder OCF₃

bedeuten.If the mixture according to the invention contains one or more compounds having a dielectric anisotropy of Δε ≥ 1.5, it is preferably one or more compounds selected from the group of the compounds of the formulas P-1 to P-4,

wherein

R

straight-chain alkyl, alkoxy or alkenyl having in each case 1 or 2 to 6 C atoms, and

X

F, Cl, CF ₃ , OCF ₃ , OCHFCF ₃ or CCF ₂ CHFCF ₃ , preferably F or OCF ₃

mean.

The compounds of the formulas P-1 to P-4 are preferably used in concentrations of 2 to 15%, in particular 2 to 10%, in the mixtures according to the invention.

, die vorzugsweise in Mengen von 2 - 15 % in den erfindungsgemäßen Mischungen eingesetzt wird.Particularly preferred is the compound of the formula

, which is preferably used in amounts of 2-15% in the mixtures according to the invention.

In addition, these liquid crystal phases may also contain more than 18 components, preferably 18 to 25 components.

In addition to the compound of the formula I-1 and / or I-2, the phases preferably contain 4 to 15, in particular 5 to 12, and particularly preferably <10, compounds of the formulas IIA, IIB and / or IIC and optionally one or more compounds the formula O-17.

Besides compounds of the formulas I-1 and / or I-2 and the compounds of the formulas IIA, IIB and / or IIC and optionally 0-17, other constituents may also be present, eg. B. in an amount of up to 45% of the total mixture, but preferably up to 35%, in particular up to 10%.

The other constituents are preferably selected from the nematic or nematogenic substances, in particular the known substances, from the classes of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenylcyclohexanes, cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalenes , 1,4-bis-cyclohexylbiphenyls or cyclohexylpyrimidines, phenyl- or cyclohexyldioxanes, optionally halogenated stilbenes, benzylphenyl ethers, tolans and substituted cinnamic acid esters.

The most important compounds which can be considered as constituents of such liquid-crystal phases can be characterized by the formula IV

R ²⁰ -LGER ²¹ IV

wherein L and E are each a carbo- or heterocyclic ring system of the 1,4-disubstituted benzene and cyclohexane rings, 4,4'-disubstituted biphenyl, phenylcyclohexane and cyclohexylcyclohexane systems, 2,5-disubstituted pyrimidine and 1,3- Dioxane rings, 2,6-disubstituted naphthalene, di- and tetrahydronaphthalene, quinazoline and tetrahydroquinazoline, G -CH = CH- -N (O) = N- -CH = CQ -CH = N (O) - -C≡C- CH2-CH2 -CO-O- -CH ₂ -O- -CO-S- -CH ₂ -S- -CH = N- -COO-Phe-COO- -CF ₂ O- CF = CF -OCF ₂ - -OCH ₂ - - (CH2) 4- - (CH ₂ ) ₃ O- or a CC single bond, Q is halogen, preferably chlorine or -CN, and R ²⁰ and R ^{21 are} each alkyl, alkenyl, alkoxy, alkoxyalkyl or alkoxycarbonyloxy having up to 18, preferably up to 8 carbon atoms, or one of these radicals also CN, NC , NO ₂ , NCS, CF ₃ , SF ₅ , OCF ₃ , F, Cl or Br.

In most of these compounds R ²⁰ and R ²¹ are different from each other, one of these radicals is usually an alkyl or alkoxy group. Other variants of the proposed substituents are in use. Many such substances or mixtures thereof are commercially available. All these substances can be prepared by literature methods.

It is self-evident to the person skilled in the art that the VA, PALC, PS-VA, IPS, PS-IPS, FFS or PS-FFS mixture according to the invention can also contain compounds in which, for example, H, N, O, Cl, F are replaced by the corresponding isotopes.

The mixtures according to the invention may furthermore contain polymerizable compounds, so-called reactive mesogens (RMs), for example in US 6,861,107 disclosed, in concentrations of preferably 0.01 to 5 wt.%, Particularly preferably 0.2 to 2% based on the mixture added. Optionally, these mixtures may also contain an initiator such as described in US 6,781,665. The initiator, for example Irganox-1076 from BASF, is preferably added to the mixture containing polymerizable compounds in amounts of 0-1%. Such mixtures can be used for so-called polymer stabilized VA modes (PS-VA) or PSA (polymer sustained VA), in which a polymerization of the reactive mesogens in the liquid-crystalline mixture is to take place. The prerequisite for this is that the liquid-crystal mixture itself contains no polymerizable components which also polymerize under the conditions where the RMs polymerize.

The polymerization is preferably carried out under the following conditions:
The polymerizable reactive mesogen (s) (RM) is (are) polymerized in a cell using a UV-A lamp of defined intensity for a defined period of time and applied voltage (typically 10V to 30V Alternating voltage, frequencies in the range of 60 Hz to 1 kHz). The UV-A light source used is typically a metal halide lamp or a high-pressure mercury lamp with an intensity of 50 mW / cm 2.

nicht polymerisieren.These are conditions where, for example, liquid crystalline compounds having an alkenyl or Alkenlyoxyseitenkette, such as. B. the compound of the formula

do not polymerize.

The mixtures according to the invention may further contain conventional additives or additives, e.g. Stabilizers, antioxidants, UV absorbers, nanoparticles, microparticles, etc.

The structure of the liquid crystal displays according to the invention corresponds to the usual geometry, as for example in EP-OS 0 240 379 , is described.

The following examples are intended to illustrate the invention without limiting it. Above and below, percentages are by weight; All temperatures are in degrees Celsius.

Throughout the patent application, 1,4-cyclohexylene rings and 1,4-phenylene rings are represented as follows:

The cyclohexylene rings are trans-1,4-cyclohexylene rings.

Tabelle 2: Brückenglieder E -CH₂CH₂- V -CH=CH- T -C=C- W -CF₂CF₂- Z -COO- ZI -OCO- O -CH₂O- OI -OCH₂- Q -CF₂O- QI -OCF₂- Tabelle 3: Seitenketten Seitenkette links Seitenkette rechts n- C_nH_2n+1- -n -C_nH_2n+1 nO- C_nH_2n+1-O- -On -O-C_nH_2n+1 V- CH₂=CH- -V -CH=CH₂ nV- C_nH_2n+1-CH=CH- -nV -C_nH_2n-CH=CH₂ Vn- CH₂=CH- C_nH_2n- -Vn -CH=CH-C_nH_2n+1 nVm- C_nH2_n+1-CH=CH-C_mH_2m- -nVm -C_nH_2n-CH=CH-C_mH_2m+1 N- N≡C- -N -C≡N F- F- -F -F Cl- Cl- -Cl -Cl M- CFH₂- -M -CFH₂ D- CF₂H- -D -CF₂H T- CF₃- -T -CF3 MO- CFH₂O- -OM -OCFH₂ DO- CF₂HO- -OD -OCF₂H TO- CF₃O- -OT -OCF₃ T- CF₃- -T -CF₃ A- H-C≡C- -A -C≡C-H Throughout the patent application as well as in the embodiments, the structures of the liquid crystal compounds are indicated by acronyms. Unless otherwise indicated, the transformation is into chemical formulas according to Tables 1-3. All radicals C _n H _{2n + 1} , C _m H _{2m + 1} , and C _{m '} H _{2m' + 1} or C _n H _2n and C _m H _2m are straight-chain alkyl radicals or alkylene radicals in each case with n, m, m ' or z C atoms.n, m, m ', z are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, preferably 1, 2, 3, 4, 5 or 6. In Table 1, the ring members of each compound are coded, Table 2 lists the bridge members, and Table 3 shows the meanings of the symbols for the left and right side chains of the compounds, respectively.

<u> Table 2: Jumper links </ u> e -CH ₂ CH ₂ - V -CH = CH- T -C = C- W -CF ₂ CF ₂ - Z -COO- ZI -OCO- O -CH ₂ O- OI -OCH ₂ - Q -CF ₂ O- QI -OCF ₂ - Side chain on the left Side chain right n- C _n H _{2n + 1} - -n -C _n H _{2n + 1} O- C _n H _{2n + 1} -O- -one -OC _n H _{2n + 1} V- CH ₂ = CH- -V -CH = CH ₂ NV C _n H _{2n + 1} -CH = CH- -nv -C _n H _2n -CH = CH ₂ Vn CH ₂ = CH- C _n H _2n - Vn -CH = CH-C _n H _{2n + 1} NVM C _n H2 _{n + 1} -CH = CH-C _m H _2m - -nVm -C _n H _2n -CH = CH-C _m H _{2m + 1} N- N≡C- -N -C≡N F- F- -F -F Cl Cl -Cl -Cl M- CFH ₂ - -M -CFH ₂ D- CF ₂ H -D -CF ₂ H T- CF ₃ - -T CF3 MO CFH ₂ O- -OM -OCFH ₂ DO- CF ₂ HO- --OD -OCF ₂ H TO- CF ₃ O- --OT -OCF ₃ T- CF ₃ - -T -CF ₃ A- HC≡C- -A -C≡CH

The mixtures according to the invention preferably contain, in addition to the compounds of the formula I-1 and / or I-2, one or more compounds of the following compounds from Table A. <b><u> Table A </ u></b> The following abbreviations are used: (n, m, m ', z: each independently 1, 2, 3, 4, 5 or 6; (O) C _m H _{2m + 1} means OC _m H _{2m + 1} or C _m H _{2m + 1} )

The preparation of the liquid crystal mixtures which can be used according to the invention is carried out in a conventional manner. In general, the desired amount of the components used in lesser amount is dissolved in the constituent of the main component, expediently at elevated temperature. It is also possible to use solutions of the components in an organic solvent, e.g. in acetone, chloroform or methanol, and to remove the solvent again after thorough mixing, for example by distillation.

By means of suitable additives, the liquid crystal phases according to the invention can be modified such that they can be used in any type of z. B. ECB, VAN, IPS, GH or ASM-VA LCD display can be used.

The dielectrics may also other, known in the art and described in the literature additives such. As UV absorbers, antioxidants, nanoparticles, radical scavengers included. For example, 0-15% pleochroic dyes, stabilizers or chiral dopants may be added. Suitable stabilizers for the mixtures according to the invention are in particular those listed in Table B.

For example, 0-15% pleochroic dyes may be added, further conductive salts, preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf., for example Haller et al., Mol. Cryst. Liq. Cryst. Volume 24, pages 249-258 (1973 )) to improve conductivity or substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases. Such substances are z. Tie DE-OS 22 09 127 . 22 40 864 . 23 21 632 . 23 38 281 . 24 50 088 . 26 37 430 and 28 53 728 described.

Tabelle C Stabilisatoren, die beispielsweise den erfindungsgemäßen Mischungen in Mengen von 0-10 Gew.% zugesetzt werden können, werden nachfolgend genannt.

n = 1, 2, 3, 4, 5, 6 oder 7

n = 1, 2, 3, 4, 5, 6 oder 7

n = 1, 2, 3, 4, 5, 6 oder 7

Tabelle D In der Tabelle D sind Beispielverbindungen zusammengestellt, die in den FK-Medien gemäß der vorliegenden Erfindung vorzugsweise als reaktive mesogene Verbindungen verwendet werden können. Sofern die erfindungsgemäßen Mischungen ein oder mehrere reaktive Verbindungen enthalten, werden sie vorzugsweise in Mengen von 0,01-5 Gew.% eingesetzt. Gegebenenfalls muss für die Polymerisation noch ein Initiator oder ein Gemisch aus zwei oder mehr Initiatoren zugesetzt werden. Der Initiator oder das Initiatorgemisch wird vorzugsweise in Mengen von 0,001-2 Gew.% bezogen auf die Mischung zugesetzt. Ein geeigneter Initiator ist z. B. Irgacure (Fa. BASF) oder Irganox (Fa. BASF).

RM-1

RM-2

RM-3

RM-4

RM-5

RM-6

RM-7

RM-8

RM-9

RM-10

RM-11

RM-12

RM-13

RM-14

RM-15

RM-16

RM-17

RM-18

RM-19

RM-20

RM-21

RM-22

RM-23

RM-24

RM-25

RM-26

RM-27

RM-28

RM-29

RM-30

RM-31

RM-32

RM-33

RM-34

RM-35

RM-36

RM-37

RM-38

RM-39

RM-40

RM-41

RM-42

RM-43

RM-44

RM-45

RM-46

RM-47

RM-48

RM-49

RM-50

RM-51

RM-52

RM-53

RM-54

RM-55

RM-56

RM-57

RM-58

RM-59

RM-60

RM-61

RM-62

RM-63

RM-64

RM-65

RM-66

RM-67

RM-68

RM-69

RM-70

RM-71

RM-72

RM-73

RM-74

RM-75

RM-76

RM-77

RM-78

RM-79

RM-80

RM-81

RM-82

RM-83

RM-84

RM-85

RM-86

RM-87

RM-88

RM-89

RM-90

RM-91

RM-92

RM-93

RM-94

RM-95

RM-96

RM-97

RM-98 Table B lists possible dopants which can be added to the mixtures according to the invention. If the mixtures contain a dopant, it is used in amounts of 0.01-4% by weight, preferably 0.1-1.0% by weight. <b><u> Table B </ u></b> In Table B possible dopants are given, which are usually added to the mixtures of the invention. Preferably, the mixtures contain 0-10 wt.%, In particular 0.01-5 wt.% And particularly preferably 0.01-3 wt.% Of dopants.

Stabilizers which can be added, for example, to the mixtures according to the invention in amounts of 0-10% by weight are mentioned below.

n = 1, 2, 3, 4, 5, 6 or 7

n = 1, 2, 3, 4, 5, 6 or 7

n = 1, 2, 3, 4, 5, 6 or 7

Table D summarizes example compounds which can be used preferably as reactive mesogenic compounds in the LC media according to the present invention. If the mixtures according to the invention contain one or more reactive compounds, they are preferably used in amounts of 0.01-5% by weight. Optionally, an initiator or a mixture of two or more initiators must be added for the polymerization. The initiator or the initiator mixture is preferably added in amounts of 0.001-2% by weight, based on the mixture. A suitable initiator is z. B. Irgacure (BASF) or Irganox (BASF).

RM-1

RM-2

RM-3

RM-4

RM-5

RM-6

RM-7

RM-8

RM-9

RM-10

RM-11

RM-12

RM-13

RM-14

RM-15

RM-16

RM-17

RM-18

RM-19

RM-20

RM-21

RM-22

RM-23

RM-24

RM-25

RM-26

RM-27

RM-28

RM-29

RM-30

RM-31

RM-32

RM-33

RM-34

RM-35

RM-36

RM-37

RM-38

RM-39

RM-40

RM-41

RM-42

RM-43

RM-44

RM-45

RM-46

RM-47

RM-48

RM-49

RM-50

RM-51

RM-52

RM-53

RM-54

RM-55

RM-56

RM-57

RM-58

RM-59

RM-60

RM-61

RM-62

RM-63

RM-64

RM-65

RM-66

RM-67

RM-68

RM-69

RM-70

RM-71

RM-72

RM-73

RM-74

RM-75

RM-76

RM-77

RM-78

RM-79

RM-80

RM-81

RM-82

RM-83

RM-84

RM-85

RM-86

RM-87

RM-88

RM-89

RM-90

RM-91

RM-92

RM-93

RM-94

RM-95

RM-96

RM-97

RM-98

In a preferred embodiment, the mixtures according to the invention comprise one or more polymerizable compounds, preferably selected from the polymerizable compounds of the formulas RM-1 to RM-98. Such media are particularly suitable for PS-FFS and PS-IPS applications. Of the reactive mesogens listed in Table D, the compounds RM-1, RM-2, RM-3, RM-4, RM-5, RM-11, RM-17, RM-35, RM-41, RM- 44, RM-62 and RM-81 are particularly preferred.

The following examples are intended to illustrate the invention without limiting it.

embodiments

Unless explicitly stated otherwise, in the present application all concentrations and% values (with the exception of the values for HR, contrast and transmission) are given in percent by weight and refer to the respective total mixture containing all solid or liquid-crystalline components, without solvent.

In the present application, all values given for temperatures such. For example, the melting point T (C, N), the transition from the smectic (S) to the nematic (N) phase T (S, N) and the clearing point T (N, I), in degrees Celsius (° C). Mp means melting point, bp = clearing point. Furthermore, K = crystalline state, N = nematic phase, S = smectic phase and I = isotropic phase. The information between these symbols represents the transition temperatures.

As a host mixture for determining the optical anisotropy Δn of the compounds, the sales mixture ZLI-4792 (from Merck KGaA) is used. used. The sales mixture ZLI-2857 is used for the determination of the dielectric anisotropy Δε. From the change in the dielectric constant of the host mixture after addition of the test compound and extrapolation to 100% of the compound used, the physical data of the compound to be tested are obtained. Depending on the solubility, the compound to be tested is usually dissolved at 10% in the host mixture.

Unless otherwise indicated, parts are by weight or percentages by weight.

Above and below mean

n _e

extraordinary refractive index at 20 ° C and 589 nm,

n _o

ordinary refractive index at 20 ° C and 589 nm,

.DELTA.n

optical anisotropy at 20 ° C and 589 nm,

ε _⊥

dielectric susceptibility perpendicular to the director at 20 ° C and 1 kHz,

ε _∥

dielectric susceptibility parallel to the director at 20 ° C and 1 kHz,

Δε

dielectric anisotropy at 20 ° C and 1 kHz,

Kp., T (N, I)

Clearing point [° C],

γ ₁

Rotational viscosity measured at 20 ° C [mPa · s], determined by the rotation method in a magnetic field,

K ₁

elastic constant, "splay" deformation at 20 ° C, [pN],

K ₃

elastic constant, "Bend" deformation at 20 ° C, [pN],

K ₃

elastic constant, "bend" deformation at 20 ° C [pN],

LTS

Low temperature stability [ L ow t emperature s tability (nematic phase)], determined in vials with 1 ml mixture, multiple determination,

HR ₂₀

"voltage holding ratio" at 20 ° C [%] and

HR ₁₀₀

"voltage holding ratio" at 100 ° C [%].

All concentrations in this application, unless explicitly stated otherwise, refer to the corresponding mixture or mixture component.

To study low temperature stability, also referred to as "LTS" (low temperature stability), i. the stability of the LC mixture against spontaneous crystallization of individual components at low temperatures, vials are stored with 1 ml FK / RM mixture at Temperaturren between 0 ° C and -30 ° C and it is checked regularly whether the mixtures were crystallized.

The VHR value is measured as follows: The FK-host mixture is optionally filled with the compound of the formula I-1 and / or I-2 and the resulting mixture in TN-VHR test cells (90 ° rubbed, orientation layer TN Polyimide (eg SE 2414 Nissan Chemicals, or AL-16301, JSR, layer thickness d ≈ 6 μm) The HR value is measured either at room temperature (RT) or after 5 min at 100 ° C before and after 0.5 h or 2 h UV exposure (suntest) at 1 V, 60 Hz, 64 μs pulse determined (measuring device: Autronic-Melcher's VHRM-105).

The so-called "helical twisting power" (HTP) refers to the helical twisting power of an optically active or chiral substance in a FK medium (in μm). Unless otherwise stated, HTP is measured in the commercially available nematic FK host mixture MLC-6260 (Merck KGaA) at a temperature of 20 ° C.

All physical properties are and have been " Merck Liquid Crystals, Physical Properties of Liquid Crystals ", status November 1997, Merck KGaA , Germany and are valid for a temperature of 20 ° C, unless explicitly stated otherwise.

Examples mix Example M1 (= Comparative Example M1)

CY-3-O2 12.00% Clearing point [° C]: 86.5 CY-3-O4 2.00% Δn [589 nm, 20 ° C]: .1092 CY-5-O2 12.00% Δε [1 kHz, 20 ° C]: -4.2 CCY-3-O1 6.00% ε _∥ [1 kHz, 20 ° C]: 3.7 CCY-3-O2 8.00% K ₃ [pN, 20 ° C]: 16.6 CCY-4-O2 8.00% K ₃ / K ₁ [20 ° C]: 1.14 CPY-2-O2 9.00% γ ₁ [mPa.s, 20 ° C]: 155 CPY-3-O2 9.00% LTS bulk (-30 ° C): > 1000 h PYP 2-3 5.00% CC-3-V1 5.00% CC-3-V 19.00% BCH-32 5.00%

To the mixture according to Example 1, the compound I-1

in unterschiedlichen Konzentrationen zugesetzt und die VHR bei den genannten Konditionen bestimmt. VHR M1 M1 + I-1 100 ppm M1 + I-1 300 ppm M1 + I-1 600 ppm VHR (60 Hz, initial, RT): 99,7 % 99,6 % 99,6 % 99,6 % VHR (60 Hz; 0,5 h Suntest, RT): 99,1 % 98,8 % 99,3 % 99,4 % VHR (10 Hz, initial, RT): 99,1 % 98,9 % 99,0 % 99,1 % VHR (10 Hz; 0,5 h Suntest, RT): 95,7 % 94,6 % 97,0 % 97,6 %

added in different concentrations and the VHR determined under the conditions mentioned. VHR M1 M1 + I-1 100 ppm M1 + I-1 300 ppm M1 + I-1 600 ppm VHR (60 Hz, initial, RT): 99.7% 99.6% 99.6% 99.6% VHR (60 Hz, 0.5 h Suntest, RT): 99.1% 98.8% 99.3% 99.4% VHR (10 Hz, initial, RT): 99.1% 98.9% 99.0% 99.1% VHR (10 Hz, 0.5 h Suntest, RT): 95.7% 94.6% 97.0% 97.6%

Example M2 (= Comparative Example M2)

CY-3-O2 12.00% Clearing point [° C]: 86.5 CY-3-O4 2.00% Δn [589 nm, 20 ° C]: .1092 CY-5-O2 12.00% Δε [1 kHz, 20 ° C]: -4.2 CCY-3-O1 6.00% ε _∥ [1 kHz, 20 ° C]: 3.7 CCY-3-O2 8.00% K ₃ [pN, 20 ° C]: 16.6 CCY-4-O2 8.00% K ₃ / K ₁ [20 ° C]: 1.14 CPY-2-O2 9.00% γ ₁ [mPa.s, 20 ° C]: 155 CPY-3-O2 9.00% LTS bulk (-30 ° C): > 1000 h PYP 2-3 5.00% CC-3-V1 5.00% CC-3-V 19.00% BCH-32 5.00%

To the mixture according to Example 2, the compound I-2

in unterschiedlichen Konzentrationen zugesetzt und die VHR bei den genannten Konditionen bestimmt. VHR M2 M2 + I-2 300 ppm M2 + I-2 600 ppm M2 + I-2 1000 ppm VHR (60 Hz, initial, RT): 99,6 % 99,6 % 99,6 % 99,6 % VHR (60 Hz; 0,5 h Suntest, RT): 97,9 % 98,8 % 98,9 % 99,0 % VHR 10 Hz, initial, RT): 98,8 % 99,0 % 98,9 % 99,0 % VHR (10 Hz; 0,5 h Suntest, RT): 89,0 % 93,9 % 94,3 % 95,1 % VHR M2 M2 + I-2 2000 ppm M2 + I-2 4000 ppm VHR (60 Hz, initial, RT): 99,6 % 99,6 % 99,6 % VHR (60 Hz; 0,5 h Suntest, RT): 97,9 % 99,0 % 99,0 % VHR 10 Hz, initial, RT): 98,8 % 98,9 % 98,9 % VHR (10 Hz; 0,5 h Suntest, RT): 89,0 % 95,2 % 94,9 %

added in different concentrations and the VHR determined under the conditions mentioned. VHR M2 M2 + I-2 300 ppm M2 + I-2 600 ppm M2 + I-2 1000 ppm VHR (60 Hz, initial, RT): 99.6% 99.6% 99.6% 99.6% VHR (60 Hz, 0.5 h Suntest, RT): 97.9% 98.8% 98.9% 99.0% VHR 10 Hz, initial, RT): 98.8% 99.0% 98.9% 99.0% VHR (10 Hz, 0.5 h Suntest, RT): 89.0% 93.9% 94.3% 95.1% VHR M2 M2 + I-2 2000 ppm M2 + I-2 4000 ppm VHR (60 Hz, initial, RT): 99.6% 99.6% 99.6% VHR (60 Hz, 0.5 h Suntest, RT): 97.9% 99.0% 99.0% VHR 10 Hz, initial, RT): 98.8% 98.9% 98.9% VHR (10 Hz, 0.5 h Suntest, RT): 89.0% 95.2% 94.9%

Analogous results for the voltage holding ratio are achieved with the mixtures according to examples M3 to M10.

Example M3 (= Comparative Example M3) The following LC mixture

CY-3-O2 22.00% Clearing point [° C]: 79.5 CY-5-O2 2.00% Δn [589 nm, 20 ° C]: 0.0942 CCOY-3-O2 8.00% Δε [1kHz, 20 ° C]: -3.0 CPY-2-O2 7.00% ε _∥ [1kHz, 20 ° C]: 3.4 CPY-3-O2 10.00% K ₃ [pN, 20 ° C]: 15.5 CCH-34 6.00% K ₃ / K ₁ [20 ° C]: 1.08 CCH-23 22.00% γ ₁ [mPa.s, 20 ° C]: 112 CCP 3-3 7.50% V ₀ [20 ° C, V]: 2.41 CCP 3-1 7.00% VHR (initial): 98.6% BCH-32 6.00% VHR (15 minUVA): 94.5% PCH-301 2.50% VHR (2 minUVA + 2h suntest): 91.6% is stabilized with 600 ppm of the compound of formula I-1.

Example M4 (= Comparative Example M4) The following LC mixture

CY-3-O2 12.00% Clearing point [° C]: 79.5 COY 3-O2 12.00% Δn [589 nm, 20 ° C]: 0.0955 CCY-3-O2 4.00% Δε [1 kHz, 20 ° C]: -3.0 CPY-2-O2 9.00% ε _∥ [1 kHz, 20 ° C]: 3.4 CPY-3-O2 10.00% K ₃ [pN, 20 ° C]: 15.3 CCH-34 6.00% K ₃ / K ₁ [20 ° C]: 1.03 CCH-23 22.00% γ ₁ [mPa.s, 20 ° C]: 108 CCP 3-3 8.00% V ₀ [20 ° C, V]: 2.39 CCP 3-1 8.00% VHR (initial): 98.4% BCH-32 6.00% VHR (15 min UVA): 93.5% PCH-301 3.00% VHR (2 minUVA + 2h suntest): 89.0% is stabilized with 1000 ppm of the compound of formula I-2.

Example M5 (= comparative example M5) The following LC mixture

COY 3-O2 21.00% Clearing point [° C]: 79.5 CCY-3-O2 3.00% Δn [589 nm, 20 ° C]: .0959 CPY-2-O2 10.00% Δε [1kHz, 20 ° C]: -3.0 CPY-3-O2 10.00% ε _∥ [1kHz, 20 ° C]: 3.5 CCH-34 6.00% K ₃ [pN, 20 ° C]: 14.9 CCH-23 22.00% K ₃ / K ₁ [20 ° C]: 1.03 CCP 3-3 8.00% γ ₁ [mPa.s, 20 ° C]: 108 CCP 3-1 8.00% VHR (initial): 98.4% BCH-32 6.00% VHR (15 min UVA): 91.0% PCH-301 6.00% VHR (2 minUVA + 2h suntest): 86.4% is stabilized with 400 ppm of the compound of formula I-1.

Example M6 (= comparative example M6) The following LC mixture

COY 3-O2 16.00% Clearing point [° C]: 81.0 CCY-3-O2 9.00% Δn [589 nm, 20 ° C]: 0.0931 CPY-2-O2 5.00% Δε [1 kHz, 20 ° C]: -2.9 CPY-3-O2 10.00% K ₁ [pN, 20 ° C]: 15.0 CCH-34 7.00% K ₃ [pN, 20 ° C]: 15.6 CCH-23 21.00% γ ₁ [mPa.s, 20 ° C]: 108 CCP 3-3 6.00% V ₀ [20 ° C, V]: 2.42 CCP 3-1 10.00% BCH-32 6.00% Y-4O-O4 7.00% CBC 33 3.00% is stabilized with 2000 ppm of the compound of formula I-2.

Example M7 (= Comparative Example M7) The following LC mixture

COY 3-O2 15.00% Clearing point [° C]: 74.5 CCOY-3-O2 5.00% Δn [589 nm, 20 ° C]: .1069 CCY-3-O2 6.00% Δε [1 kHz, 20 ° C]: -3.0 CPY-2-O2 8.00% K ₁ [pN, 20 ° C]: 14.0 CPY-3-O2 10.00% K ₃ [pN, 20 ° C]: 14.7 CCH-23 24.00% γ ₁ [mPa.s, 20 ° C]: 104 CCH-34 5.00% V ₀ [20 ° C, V]: 2.34 PYP 2-3 10.00% PYP 2-4 5.00% CC-3-V1 10.00% PCH-301 2.00% is stabilized with 2000 ppm of the compound of formula I-2.

Example M8 (= comparative example M8) The following LC mixture

CC-3-V 32.00% Clearing point [° C]: 75 PP-1-3 2.30% Δn [589 nm, 20 ° C]: .1021 CC-3-V1 6,70% Δε [1 kHz, 20 ° C]: -3.7 PY-3-O2 8.10% K ₁ [pN, 20 ° C]: 12.9 PY-V2-O2 7.35% K ₃ [pN, 20 ° C]: 15.5 CEY-3-O2 2.75% γ ₁ [mPa.s, 20 ° C]: 96 CCP-V-1 4,60% V ₀ [20 ° C, V]: 2.15 CCY-V O1 5.60% CCY-V O2 9.40% CPY-V O2 4.80% CAIY-3-O2 6.85% CCY-V O4 7,60% CPY-V O4 1,95% is stabilized with 2000 ppm of the compound of formula I-2.

Example M9 The following LC mixture

CC-3-V 36.50% Clearing point [° C]: 75 CC-3-V1 2.00% Δn [589 nm, 20 ° C]: 0.1015 CCY-3-O1 8.00% Δε [1 kHz, 20 ° C]: -3.7 CCY-3-O2 6.00% K ₁ [pN, 20 ° C]: 13.8 CCY-4-O2 2.50% K ₃ [pN, 20 ° C]: 15.0 CLY-3-O2 8.00% γ ₁ [mPa.s, 20 ° C]: 97 CLY-3-O3 2.00% V ₀ [20 ° C, V]: 2.14 CPY-2-O2 10.00% CPY-3-O2 3.00% CY-3-O2 5.50% PY-3-O2 13.00% PY-1-O4 3.50% is stabilized with 2000 ppm of the compound of formula I-2.

Example M10 (= Comparative Example M9) The following LC mixture

CC-3-V 31.50% Clearing point [° C]: 75.5 PP-1-3 4.50% Δn [589 nm, 20 ° C]: .1086 CC-3-V1 3.30% Δε [1 kHz, 20 ° C]: -3.7 PY-3-O2 6.00% K ₁ [pN, 20 ° C]: 12.9 PP 1-5 1.50% K ₃ [pN, 20 ° C]: 15.2 PY-V2-O2 7.00% γ ₁ [mPa.s, 20 ° C]: 101 CEY-3-O2 3.70% V ₀ [20 ° C, V]: 2.14 CCY-V O1 5.50% CCY-V O2 10.00% CPY-V O2 5.70% CAIY-3-O2 7.00% CCY-V O4 7.40 CPY-V O4 4.70 GPP 5-2 2.20 is stabilized with 2000 ppm of the compound of formula I-1.

Claims (15)

1. Liquid-crystalline medium based on a mixture of polar compounds, characterised in that it comprises a compound of the formula I-1 and/or I-2

   

   where the proportion of compounds of the formula I-1 or of the formula I-2 in the mixture as a whole is 50 - 10000 ppm, based on the mixture,
   and
   additionally one or more compounds selected from the group of the compounds of the formulae IIA, IIB and IIC,

   

   

   

   in which

   R^2A, R^2B and R^2C in each case, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups in these radicals may be replaced by -O-, -S-,

   

   -C≡C-, -CF₂O-, -OCF₂-, -OC-O- or -O-CO- in such a way that O atoms are not linked directly to one another,

   L^1-4 in each case, independently of one another, denote F, Cl, CF₃ or CHF₂,

   Z² and Z^2' in each case, independently of one another, denote a single bond, -CH₂CH₂-, -CH=CH-, -CF₂O-, -OCF₂-, -CH₂O-, -OCH₂-, -COO-, -OCO-, -C₂F₄-, -CF=CF-, -CH=CHCH₂O-,

   p denotes 0, 1 or 2,

   q denotes 0 or 1, and

   v denotes 1 to 6,

   and the medium additionally comprises one or more compounds selected from the group of the compounds of the formulae L-1 to L-11, the terphenyls of the formulae T-1 to T-21 and the compounds of the formulae BF-1 and BF-2,

   

   

   

   

   

   

   

   

   

   

   

   in which

   R, R¹ and R² in each case, independently of one another, have the meanings indicated for R^2A and alkyl denotes an alkyl radical having 1-6 C atoms, and

   s denotes 1 or 2,

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   in which

   R denotes a straight-chain alkyl or alkoxy radical having 1-7 C atoms and

   m denotes 1-6,

   

   

   in which

   R¹ and R² in each case, independently of one another, have the meaning of R^2A,

   c denotes 0, 1 or 2,

   d denotes 1 or 2.
2. Liquid-crystalline medium according to Claim 1, characterised in that it comprises one or more compounds of the formulae

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   in which alkyl and alkyl* in each case, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms and alkenyl denotes an alkenyl radical having 2-6 C atoms.
3. Liquid-crystalline medium according to Claim 1 or 2, characterised in that the medium additionally comprises one or more compounds of the formula III,

   

   in which

   R³¹ and R³² in each case, independently of one another, denote a straight-chain alkyl, alkenyl, alkoxy, alkoxyalkyl or alkoxy radical having up to 12 C atoms, and

   

   Z³ denotes a single bond, -CH₂CH₂-, -CH=CH-, -CF₂O-, -OCF₂-, -CH₂O-, -OCH₂-, -COO-, -OCO-, -C₂F₄-, -C₄H₉-, -CF=CF-.
4. Liquid-crystalline medium according to one or more of Claims 1 to 3, characterised in that the medium additionally comprises one or more compounds of the formulae 0-1 to 0-18,

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   in which
   R¹ and R² in each case, independently of one another, have the meanings indicated for R^2A in Claim 1.
5. Liquid-crystalline medium according to one or more of Claims 1 to 4, characterised in that the medium additionally comprises one or more compounds selected from the group of the compounds of the formulae O-6, O-7 and O-17,

   

   

   

   in which
   R¹ denotes alkyl or alkenyl having 1-6 or 2-6 C atoms respectively and R² denotes alkenyl having 2-6 C atoms.
6. Liquid-crystalline medium according to one or more of Claims 1 to 5, characterised in that the medium additionally comprises one or more indane compounds of the formula In,

   

   in which

   R¹¹, R¹², R¹³ denote a straight-chain alkyl, alkoxy, alkoxyalkyl or alkenyl radical having 1-5 C atoms,

   R¹² and R¹³ additionally also denote halogen,

   

   

   i denotes 0, 1 or 2.
7. Liquid-crystalline medium according to one or more of Claims 1 to 6, characterised in that the medium additionally comprises at least one polymerisable compound.
8. Liquid-crystalline medium according to one or more of Claims 1 to 7, characterised in that the medium additionally comprises one or more additives.
9. Liquid-crystalline medium according to one or more of Claims 1 to 8, characterised in that the additive is selected from the group free-radical scavenger, antioxidant and/or stabiliser.
10. Liquid-crystalline medium according to one or more of Claims 1 to 9, characterised in that the medium comprises one or more stabilisers selected from the group

    

    

    n = 1, 2, 3, 4, 5, 6 or 7

    

    n = 1, 2, 3, 4, 5, 6 or 7

    

    n = 1, 2, 3, 4, 5, 6 or 7

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    
11. Liquid-crystalline medium according to one or more of Claims 1 to 10, characterised in that the medium comprises one or more stabilisers in amounts of 0-10% by weight.
12. Process for the preparation of a liquid-crystalline medium according to one or more of Claims 1 to 11, characterised in that the compound of the formula I-1 and/or the compound of the formula I-2 is mixed with at least one compound selected from the group of the compounds of the formulae IIA, IIB and IIC and additionally one or more compounds selected from the group of the compounds of the formulae L-1 to L-11, T-1 to T-21, BF-1 and BF-2 and with at least one further liquid-crystalline compound,
    and optionally one or more additives and optionally at least one polymerisable compound are added.
13. Use of the liquid-crystalline medium according to one or more of Claims 1 to 11 in electro-optical displays.
14. Electro-optical display having active-matrix addressing, characterised in that it comprises, as dielectric, a liquid-crystalline medium according to one or more of Claims 1 to 11.
15. Electro-optical display according to Claim 14, characterised in that it is a VA, PSA, PA-VA, PS-VA, PALC, IPS, PS-IPS, FFS, UB-FFS or PS-FFS display.